DE2508059A1 - CYCLOALIPHATIC UNSATURATED ESTERS AS FLAVORS AND PERFUMES - Google Patents

Description

DIPL.-INQ. DIETER JANDER DR.-INQ. MANFRED BÖNINQ

PATENT LAWYERS Delivery address:

reply to:

8 MONKS 80 (ARCH HOUSE)

KOLBERGER STRASSE 21 ' ^{BERLIN 15}

Telephone: 089/98 27 04 KURFDRSTENDAMM 66

Telephone: 030/8835071 Telegrams: Consideration Berlin

97 / 15.492 EN

February 21, 1975

Patent application

of the company

NAARDEN INTERNATIONAL N.V. Huizerstraatweg 28 NAARDEN, Netherlands

"Cycloaliphatic Unsaturated Esters as Flavors and fragrances "

The invention relates to new chemical compounds and their use as flavorings and fragrances. In particular concerns they are cycloaliphatic unsaturated esters, which are valuable food and tobacco flavorings and fragrances for perfumes are.

509836/1026

^ w ** ■ Postal check account Berlin West Account 174384-100 Berliner Bank AG .. Account 01 10921900

DIPL-INq. DIETER JANDER DR.-INQ. MANFRED BONINQ _M

PATENTANWÄLTE 2 5 Ü 8959

There is growing attention to the manufacture and use of synthetic fragrances and fragrance modifiers Dedicated to fabrics for perfumes and perfumed products. The same applies to synthetic materials and to the taste modifiers for food, beverages, pharmaceuticals and tobacco. This increasing attention does not move therefore that the amount of natural fragrances and substances, which is available is not sufficient, but perhaps to an even greater extent because of the great need for substances consists that can combine different natural nuances, blend better with other fragrances or flavors mix and result in perfumed or flavored products that are specially designed for a specific purpose and which can be produced in any quantity as desired. This latter factor is a great advantage for synthetic fragrances and te for food, as natural products such as essential oils, extracts, concentrates u * like. due to deviations in quality, in type or major changes in the treatment of the starting material subject.

The S3 Ir finding refers to saffron acid and Bster their homologues and their use as flavorings and fragrances.

There are three isomeric forms of safreusic acid, the £ - and ^ - saffron acid
or »III have:

- and ^ - Saffron acid are known and which have the formulas I, II

509836/1026

Γ Ϊ ^f

DIPL-INQ. DIETEK JANDER DR.-INQ. MANFRED BONINQ

For convenience, when naming the various compounds of the present invention, in In analogy to the isomers of saffron acid, the following nomenclature is used throughout the application:

- = conjugated double bonds in positions 2 (endocyclic)

and 4

e «» «nit

r = "" ti ti η 2 (exocyclic)

and 3.

<* - Saffron acid is described in HeIv. Chim. Acta 21 »134 (1948), ^ 3-Saffron Acid in Reports 24 »1242 (1941), and <* .- and ^ - Saffron Acid will be in HeIv. Chim. Acta 22 »1746 (1950) mentioned.

Some methyl and ethyl esters of saffron acid are also described in the literature:

- Ethyl saffronate in HeIv. Chim. Acta 21 »134 (1948);

- Methyl-c * - and - ^ f-safranate and ethyl - «/« - and - y-safranate will be in HeIv. Chim. Acta 22 »1746 (1950) mentioned;

- The production of ethyl-15-saffranate is in HeIv. Chim. Acta 28 »1863 (1955) given;

- Methyl- β- saffronate is in Compt. Rend. Ser. C 262, 1725 (1966), in Bull. Soc. Chim. France 1966, 3874 and in Agr. Biol. Chem. 2it »198 (1970) mentioned;

- The production of ethyl-ol-, -ß- and -y-saffranate is in HeIv. Chim. Acta £ 4, 1767 (1971);

- Esters of e-, ft- and ^ T-saffron acid with saturated alcohols with 1-4 carbon atoms are also mentioned in NL-OS 72.11248 and 73.01451, which were published on August 17, 1972 and August 7, 73 respectively.

5098 3 6/1026

DIPL-INq. DIETER JANDER DR.-INQ. MANFRED BDNINC

PATENTANWÄLTE 2 5 Ö 8 Ü 5 9

In these publications the saffranates are used as intermediate products for the production of Safranal, Damascenones and abscisic acid are used. Nowhere, however, is anything mentioned about the organoleptic properties of these Ester said something.

It has now been found that the saffron acid esters and some new homologues thereof possess useful organoleptic properties and can be used in a variety of ways to give flavor and fragrance to products. The invention Compounds - in combination with other flavorings, thinners or carriers - can be used for this purpose add flavor to food, beverages or tobacco products; you can use other fragrances be used to make fragrance compositions, as is customary in perfumery.

The fragrant esters according to the invention have the general formula

IV

wherein the dashed lines represent two conjugated double bonds in the positions 2-endocyclic and 4 (d -isomer), 1 and 3 (β -isomer) or 2-exocyclic and 3 (^ -isomer) and R _{1 is} an alkyl group or in the y ^ Isomers denote an alkylidene group with 1-3 carbon atoms each and R ₂ denotes an alkyl or alkenyl group with 1-4 carbon atoms.

The compounds of the formula IV in which R _{1 is} a CH ^ group (oC or § isomers) or a CH ₂ group (^ isomers) and R _{2 is} a methyl or ethylene group are known compounds, they are the methyl and ethyl safranate described in the literature cited above. The other compounds of the formula IV are new.

509836/1026 - 5 -

DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ

The compounds according to the invention can by methods are prepared, which are given in the literature mentioned for the homologues of the saffron acid esters. The method ^ which are described in the examples represent modifications of the method described in NL-OS 73.01451, pages 11-13 is indicated and after the theoC, | S- and - ** ~ saffron acid ethyl ester from mesityl oxide and ethyl acetoacetate according to reaction scheme A as intermediate products in the production represented by dasmascenon analogs:

REACTIONS SCHEME A ■. ..

It has now been found that the ratio of ET-ß, and Tj-- isomers in the final stage it can be ReaktioneJB-ge varied by changing the reaction time to one another. If you start from acetoacetic acid alkyl or alkenyl esters, you normally get a mixture of the compounds IV (with R ₁ = CH, or CH ₂ ), consisting mainly of the / ^ isomers (about 6056) and about 20J6 each of the < £ - and J ^ isomers.

In the preparation of the compounds of the general formula IV in which R ₁ denotes a radical with two or three carbon atoms, an increase in the reaction time in the dehydrogenation stage leads to the formation of a reaction mixture which consists of more than 9056 of the r-isomer. Its shorter dehydrogenation time leads to a higher content of denu and / 3 isomers, although the 7 "isomer is the main component in the mixture obtained. The three isomers of the compounds of the general formula IV can be prepared by preparative gas-liquid The preparation of the compounds according to the invention is carried out in Example 1 by means of the synthesis of a mixture of the ccc, fi and ^ isomers of the compound of the formula IV, in which R ₁ = C ₂ H ^ (o ^ - or /? - isomers ) or C ₂ H ^ (r - isomer) and R ₂ = C ₂ H ^ is shown.

509836 / 102Ö

DIPL.-INQ. DIETERJANDER DR.-INQ. MANFRED BONINO

PATENTANWÄLTE 2 5 Ö 8 Ü 5 9

By changing R ₁ and R ₂ in the condensation reaction between mesityl oxide and acylacetic acid ester (cf. reaction scheme A), further compounds of the general formula IV can be prepared. It is clear to the person skilled in the art that other methods for reducing the cyclohexanone can also be used (for example the Meerwein-Ponndorf reduction). Examples of this can be found in the cited parts of the literature.

The following compounds of the general formula IV were prepared analogously to the method given in Example 1:

^R 1 CH ₀ R ₂ boiling point
in ⁰ C "20th
ⁿ D CHj or CK ₃ 37-40 / 3 mm Ed 1.4820 id ^C 2 ^H 5 70-76 / 5 mm Ed 1.4790 id CH ₂ CH = CH ₂ 78-79 / 2 mm Ed 1.4884 id C ₃ E ₆ CH ₂ CH (CH ₃ ) ₂ 68-73 / 2 mm Ed 1.4747 C, H «or C ₂ H ₅ 78-82 / 3 mm Ed 1.4832

As already mentioned, all reaction products contain eC «, ß and T'-Isoffiere. Di s T-isomer of formula IV in which R ₁ contains two or three Korilenstoffatoae, exist in two geometriechen Isomären "the cis and trens-Iaoiaeren, as shown in dsn fei constricting both formulas (IV ait R ₁ ■ * S ₂ H ^) s

509836/1020

DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ

The amounts of the two J isomers that are formed according to the sequence of reactions described are largely the same.

It has been shown that the compounds according to the invention have very advantageous organoleptic properties. Although there are minor differences in their fragrance and taste character, it is not always necessary that To separate isomers because the mixture of isomers can be used as such for the purposes of the invention. The isomers have strongly related smells, as can be seen from the following fragrance descriptions, those of experienced ones Fragrance and flavor experts come from.

- Ethyl saffronate (mixture <* ■: β : T = 20: 60: 20) (formula IV,

R ₁ = CH ₅ or CH ₂ , R «C ₂ H ₅ ):

The main impression of this mixture can be herbal, spicy (rosemary, ears of wheat, bay leaf) and fruity (apple, plum) can be reproduced with a certain undertone of roses and wood.

- ethyl cL-safranate (formula IV-OS Rp CH ₃ , R ₂ = C ₂ H ₅ ); The woody, ion-like undertone is somewhat more pronounced than in the mixture of the three isomers.

Ethyl- ρ- saffronate (formula IV- B, R ₁ = CH ₃ , R ₂ = C ₂ H ₅ ): The herb-like, spicy character is more pronounced, although there is a great similarity with the mixture.

Ethyl- T- saffronate (formula IV-T ", R ₁ = CH ₂ , R ₂ = C ₂ H ₅ ): A more fruity character (apple, plum) can be observed, the difference to the mixture of the three isomers is slight .

503836/1026

DIPL.-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ

Methyl saffron (mixture) (formula IV, R ₁ = CH ₃ or CH ₂ , R ₂ = CH,) has a less fruity character than ethyl saffron. The herb-like spicy notes are stronger. In the aftertaste it has some lovely Tonke notes

- Allylsafranate (mixture) (Formula IV, R ₁ = CH ₃ or R ₂ = C ₃ H ₅ ):

The character of the fragrance is almost identical to Ethylsafranat, but less intense.

- Isobutyl saffronate (mixture) (Formula IV, R ₁ = CH ₃ or CH ₂ , R ₂ = 1-C ₄ H ₉ ):

The main directions are herbal, spicy with a striking pear-like character. The mixture is suitable especially suitable for taste purposes.

- Ethyl 6,6-di ^ methyl-2-ethylidene-3-cyclohexenecarboxylate (formula IV, R ₁ = C ₃ H ₄ , R ₂ = C ₂ Hr): The fragrance of this ester is very similar to ethyl safranate, but the fragrance intensity is probably a bit stronger.

- Ethyl-6, ö-dimethyl ^ -propylidene ^ -cyclohexencarboxylat (formula IV, R ₁ = C ₃ Hg, R ₂ = C ₂ Hc): Compared to ethyl saffron, the odor intensity is much lower. The fruity notes of ethyl saffron have almost completely disappeared, but the herb-like, spicy notes are much stronger. This ester also shows an earthy-woody note.

The fragrance descriptions can provide some general information on the usefulness of the compounds according to the invention. However, the compounds are almost always used in combination with other flavors and fragrances. One can in In no case can foresee whether a compound with a particular fragrance will turn out to be satisfactory in fragrance or fragrance

509836/1028

DIPL-INO. DIETER JANDER DR.-INQ. MANFRED BONINQ

Flavor compositions behaves. It is further sufficient for a substance that is used as a fragrance or flavor component should be used, does not mean that it only has fragrance. Some other requirements are:

- Compatibility with other fragrances and flavors as well as with the substrate, which is provided with a fragrance or taste shall be;

- favorable toxicological and dermatological properties;

- the ability to create complex fragrance or flavor compositions according to the ideas of a skilled fragrance or flavor expert, a general one To give character or a specific touch.

The compounds of this invention meet these requirements.

When assessing compounds for their possible use in fragrance or flavor compositions, the threshold levels are often determined. Since the compounds of this invention very well with the known damascones and damascenones, which are described, for example, in GB-PS 1.240.309 and in NL-OS 72.11248, and with the homologues of the damascene and damascenones, which are described in our patent application ... ... ..f are specified fit, the limit values of all these compounds and some mixtures thereof were determined «The method used for this is described in the Manual on Sensory Testing Methods, ASTM Special Technical Publication No. 434, Philadelphia, 1968, page 30, method 3b and on page 61. In order to show some peculiarities of the compounds according to the invention and the interactions of these compounds with other fragrances and flavors, the results of these experiments are shown in the following table:

*) Parallel registration from the same day, us. Sign: 97/15 486 DE

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509836/1 026

DIPL.-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ PATENT LAWYERS

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description

link

Basic threshold ^a 'practice of the

Fragrance

A. Ethyl saffron (mixture)
£ 1 ^ ijr «.2O: 60: 20 6: κ ΙΟ " ⁶ generally
fruity,
but not
apple-like B. Ethyl-6,6-dimethyl-2-ethyl-
idene-3-cyclohexene carboxylate 10 χ 10 " ⁶ apple-like C. c <—Damascon ^c ' 1 χ 10 " ⁶ apple-like D. P-Damascenon ' 6th χ 10 " ⁶ apple-like

Damascenon homologues s

8 χ 10

-6

near d. Threshold value:
fruityj in higher
Concentrate jor coffee-like fc

Damascone homologues ' 0, 8x10 "" ⁶ apple-like
ί F. A + E (5 ί 2) 0, 2x1Ο " ⁶ clear
apple-like G B + E (5: 2) 2 χ 10 " ⁶ apple-like H A + D (5: 2) O, 6-10 " ⁶ apple-like I.

Notesί

a) All compounds and mixtures were in colorless diethyl phthalate solved.

b) The threshold values were determined by lay observers who were asked to give a general description of the fragrance. The descriptions in the table are very different from those given by experts.

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DIPL-INq. DIETER JANDER DR.-INQ. MANFRED BONINQ

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c) s = trans-2,6,6-trimethyl-1-crotonyl-2-cyclohexene, cf. GB-PS 1,240,309

d) = trans-2,6,6-trimethyl-i-crotonyl-i, 3-cyclohexadiene, see GB-PS 1,240,309

e) s reaction product of example 9 of our patent application No

f) = "η η 8" " No

From this table it can be seen that the mixtures G, H and I have significantly lower threshold values than the individual ones Components. This is probably the first time there has been synergy in this area from quantitative data could be proven. Just as striking is the fact that the combination of compounds A and B has a certain effect has an apple-like odor, while the individual components on their own have a general fruit-like odor that does not resemble the scent of apples.

It follows that the esters according to the invention - when they are in combination with cycloaliphatic unsaturated ketones like «--Damascon, ß-Damascenon or one or more homologues of which, which are described in German patent application no

are used - specifically enhance the fragrance and flavor properties of these ketones, whereby optimal taste and fragrance effects can be achieved. The esters, like the ketones, can be mixtures of isomers represent. In order to obtain these remarkable effects, the relative amounts of the invention Esters and the unsaturated ketones vary between about 1:10 and about 10: 1.

It is clear to the person skilled in the art that when using flavors and fragrances it is neither possible nor practicable is to provide specific instructions for the use of the

509836/1026 - 12 - ■

DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ

PATENT LAWYERS 25 08 Ü 59

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appropriate Sster - neither alone, nor in combination with the ketones mentioned - to give in these areas, because too many factors determine the absolute amounts of substances to be used. About these factors include the personal preference of the flavor or fragrance expert, the cost of materials, the nature of the special Composition, the taste or fragrance effect to be achieved, etc. Nonetheless, it is for the It is completely clear to the person skilled in the art how he will use the esters according to the invention in the individual situations.

Fragrance compositions that the Sster according to the invention can be used in a large number of perfumed substances. For example, they can be used in soaps, Detergents, deodorants, in cosmetic preparations such as colognes, toilet water, face creams, body water, Talcum powder, sun block, and aftershave can be used. Flavor compositions that the invention Containing esters can be used to flavor foods, beverages, medicines or tobacco. the Esters can also be used to improve the taste of beverages such as fruit juices.

The invention is illustrated in more detail in the following examples explained. All quantitative data in Examples 2-11 are based on weight. The examples are intended to enhance the invention only explain, not restrict in any way.

example 1

A. Manufacture of
hexene carboxylate.

A mixture of 294 g of mesityl oxide, 432 g of c ^ -propionyl acetic acid ethyl ether, 150 g of cyclohexane and 75 g of zinc chloride was used Stirred for 60 hours at the boiling point of the mixture. The water ··, welelies through «lie üsalstiün, was through

Q η α α ο ο. Ιη-. ,> _Λ ■ *

DIPL-INQ. DIETER JANDER DR-INQ. MANFRED BONINC

PATENT ADVERTISER, 25Ö8059

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a Dean-Stark tube derived. The mixture obtained was treated with 300 g of a 1Oxigen HCl solution at room temperature for 10 minutes and 150g of cyclohexane stirred. After washing with water, one NaHCO-2 solution and again water was the cyclohexane from the separated organic layer distilled off and the residue fractionated in vacuo. This resulted in 272 g of one Product, bp 126-135 ° C / 2 Torr, n | ° = 1.4788, which according to gas-liquid chrometography and NMR analysis 9096 from ethyl 6, o-dimethyl ^ -äthyl ^ -oxo ^ -cyclohexencarboxylat duration.

B. Making a mixture of

Ethyl-6, ö-dimethyl ^ -äthyliden ^ -cyclohexencarboxylat, ^{n nw} "-äthyl-i ^ -cyclohexadiencarboxylat and w η 11 μ 11 _2 4 ^{w M w} .

A solution of 25g NaBH ^ and 0.25g NaOH in 100g water was added dropwise to a solution of 270g ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexenecarboxylate in 100g ethanol. During the addition, the reaction vessel was cooled to 35-40 ° C. The reaction mixture was stirred for a further 4 hours without cooling, the temperature in the reaction vessel slowly reaching room temperature. The reaction mixture was diluted with 200 ml of toluene and washed with 100 ml of 10% acetic acid. The organic phase was separated off and dried. Then 2 g of p-toluenesulfonic acid were added and the mixture was refluxed for 2 hours. ¹ 'After washing with a 5 # aqueous NaHCO ^ solution and water, the volatile solvent was removed in vacuo, and 263g of an oily liquid remained, which was fractionally distilled. The second fraction of the distillate (I67g) had a boiling point of 74-90 ° C / 2 Torr

20th
and the refractive index n £ = 1.4819. It consisted of a mixture of the three compounds named in the heading, and indeed contained 1596 ° C. isomer, 596 ° C. isomer and 8096 ° isomer.

1) Do you leave the mixture? Hours under reflux sladea, the r-isomer (b.p. 77 * S0 ° C / 2 Torr, n ² | * 1, ^ 835) is the only reaction product,

5Ü9836 / 1026 ₁₄

DIPL.-INO. DIETER JANDER DR.-INQ. MANFRED BONINQ

PATENT LAWYERS 2508

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Example 2

Rose-type perfume composition.

Three rose-type perfume compositions were made by mixing

made of the following components:

Composition ingredient
Cinnamon alcohol
Phenylethyl alcohol
Rhodinol
1-citronellol

Phenylacetaldehyde dimethylacetal qL -Methyljonon
Hydroxycitronellal

Gyrane (N), fragrance available from Naarden International N.V.

Phenylethyl propionate Geranyl acetate

Citrellyl ethyl oxalate Eugenol, 10 # solution in

Diethyl phthalate

Undecenal, 10 $ solution in 5-5

Diethyl phthalate

Rose oxide , 10 # solution in 5 5 5

Diethyl phthalate

J -Methyljonon 10

Linalool - 10

Lauric aldehyde, 10% solution in 10

Diethyl phthalate

Rosana NB 131? Rosenbase available from

Naarden International N.V. - 5

Geranium oil Bourbon - - 10

Rust absolute, 10 $ ige Lßsrj & g in

diethyl phthalate ₌ - 5

995 995 99o

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3098 ^ 0/1 ^ 26

A. B. C. 15th 20th 5 400 3Θ0 435 260 280 25ο 160 140 150 40 50 25th 15th - 5 5 - 10 30th 20th 15th 15th 30th 25th 10 20th 30th 20th 10 5 15th VJI 10

DIPL-INO. DIETER JANDER DR.-INQ. MANFRED BONINQ

PATENTANWÄLTE 2 5 Ü8 Ü5 9

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A. By adding 0.5g of a 1 # solution of ethyl saffronate in diallyl phthalate to 99.5 g of mixture A the composition becomes more brilliant than the original mixture and receives a more pronounced one natural rose character with a pronounced fruity top note.

B. By adding 0.5g of a 1 # solution of ethyl 6,6-dimethyl ^ -äthyliden ^ -cyclohexencarboxylat in diethyl phthalate to 99.5g d & r mixture B is the composition instantly stronger and fuller. The mixture received an unusual brilliance and a flowery lifelike Rose character.

C. By adding 1 g of a 1 # solution of ethyl 6,6-diemthyl-2-propylidene-3-cyclohexenecarboxylate For 99g of mixture C, the mixture received a greater fullness and a more pronounced natural note than the starting mixture.

Example 3

Fougdre type perfume composition. Three Fougere-type perfume compositions were made by Mixing the following ingredients made:

Composition ingredient
Coumarin
Musk ketone
Phenylethyl alcohol
Oak moss absolutely
Amyl salicylate
Rosemary oil
Serpolet oil

-.16 -

509836/10 26

A. B. C. 30th 25th 15th 5 VJl 10 80 90 100 10 10 5 30th 20th 40 30th 35 40 10 15th 20th

. DIETER JANDER DR.-INQ. MANFRED BONINQ

PATENT Attorneys ^ 5 0 8 0 5 9

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AWAY

260 255 220 100 60 120 40 60 30th 10 15th 5 Oil 10 5 5 5 - 5 10 10 20th 25th 20th 20th 30th 40 10 Oil 15th 70 50 15th - 5 - _ 10 Oil - 5 - - - 10 740 745 785

LavenderBl, French style Bergaaottessenz Lemon oil eugenol

Ylang-ylang oil Coriander oil, clary ointment! Oil Geranium oil bourbon

Musk R1, fragrance available from Naarden International N.V., 10 # solution in diethyl phthalate

Undecenal, 10 # solution in diallyl phthalate Linalool

Methyl nonyl acetaldehyde, 10 # solution in

Diethyl phthalate

J -Methyl;) onon

Tetradecanal, 1 # solution in diethyl phthalate

Thyme oil, 10 # "« »

A. After adding 1g of a 1 ^ solution of ethyl saffron in Diethyl phthalate to 74 g of mixture A shows a considerable increase in brilliance. The composition becomes stronger in character and receives a strikingly fruity note.

B. By adding 0.5 g of a 1 # solution of ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate in diethyl phthalate to 74.5 g of mixture B, the composition becomes stronger and fuller. The mixture gets a greater brilliance and the character of the perfume is emphasized.

C. By the addition of 1.5 g of a 1 # solution of ethyl-6,6-diinethyl-2-propylidene-3-cyclohexenecarboxylate in diethylphthalate

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DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BONINC

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To 78.5g of mixture C, the fragrance character of this mixture has a fuller and warmer core and a considerable one There is a noticeable increase in brilliance.

Example 4

Pine Fancy Type Perfume Composition · Three pine fancy type perfume compositions were made made by mixing the following ingredients:

Composition ingredient
Frankincense Resinoid
Elemi oleoresin
Bornyl acetate liquid
Turpentine oil, distilled
Orange oil terpenes
Rosemary oil, French
Guaiyl acetate

Cistue absolut, 10 # solution in diallyl phthalate 10-10

Methyl nonyl acetaldehyde, 10J) 4 solution in

Diethyl phthalate 30 AO 25

Ligustral (N), fragrance available from Naarden International N.V., 10 # ige Solution in diethyl phthalate

Wacholderbeer91 oak moss absolute, 10 # solution in

Diethyl phthalate

Thyme oil, 10% solution in diethyl phthalate Serpolet oil Origanum oil Synthetic geranium oil Lavender oil, French Bay leaf oil

A. B. C. 20th 10 10 20th 25th 10 550 580 600 130 100 110 150 120 135 5 20th 20th 15th 10 10

20th - 15th VJl 20th - 30th 20th 20th - 25th 10 5 - - - - 20th - ■■■■ Ml
995 - 10 - VJl - 5 - 5 995 990

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DIPL-INQ. DIETER JANDER DR.-1NQ. MANFRED BONINQ

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A. The addition of 5g of a 1% solution of ethyl saffron in Diethyl phthalate for mixture A (995g) leads to a remarkable increase in brilliance and natural fullness this composition.

B. The addition of 5g of a 1 # solution of ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate in diethyl phthalate to 995g of mixture B leads to a fuller, warmer character this composition, to a greater brilliance and stronger emphasis on the warm herbal notes.

C. By adding 10 g of a 1 # solution of ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate in diethyl phthalate to 99O g of mixture B, a composition is obtained with a stronger full natural character.

Example 5

Making an apple flavor imitation. An apple flavor imitation was made by mixing the following Components manufactured:

Amyl acetate 35 Ethyl butyrate 15th Hexyl acetate 3 Amyl propionate 1 Orange Oil Florida 0.4 Ethanol 96 # ig 945.6

1,000

An apple drink was made by using 0.3g of this flavor composition per 1 finished drink. Two modifications of the apple flavor composition were made by adding 25 and 50 ppm ethyl saffronate, respectively, to the composition prepares.

These two modified apple drinks were mixed with the unmodified drink by a group of taste experts

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DIPL.-INQ. DIETER JANDER DR-INQ. MANFRED BONINQ

PATENT LAWYERS 2 5 O 8 O 59

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resembled. All members of this group clearly preferred the drinks that contained an addition of ethyl saffronate, as these looked more like natural apples in terms of smell and taste. No significant difference was made between made the two drinks with ethyl saffron, although the difference in concentration was announced.

From this example it can be seen that the concentration of ethyl saffronate in the finished beverage is well below the fragrance threshold of the pure compound. Still it is Influence on the fragrance and the taste of the drink can be clearly determined. (25 ppm in the composition; 0.3g the Composition per 1 drink; this results in the concentration of ethyl saffron in the drink at 7 »5 · 10 g / l ·)

Example 6 Making a composition with mimicked apple flavor. Its composition with mimicked apple flavor was made after L. Benezet, La Parfumerie Moderne 43 (1951) No. 22, 61-78

manufactured:

Ethyl acetate 50 Ethyl acetoacetate 200 Ethyl formate 20th Ethyl butyrate 50 Ethyl hexanoate 20th Ethyl heptanoate 50 Ethyl octanoate 20th Isoamyl formate 50 Isoamyl acetate 50 Isoamyl pentanoate 100 Isoamyl hexanoate 50 Isoamyloctanoate 100 acetaldehyde 50 Geraniol 10 Geranyl formate 10 Geranyl acetate 10 Phenyl ethyl pentanoate 20th

B09836 / 1026 -20-

DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BONINO

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Benzaldehyde 5

Cinnamyl propionate 50

Diethyl malonate 64

Orange Oil Florida 20

Rose oil 1

1,000

A 1 # solution in ethanol was prepared from this mixture. Part of this solution was used to make an apple drink, 0.3 g of the ethanol solution used per 1 finished drink.

Another part of the ethanol solution was 100 ppm of ethyl saffronate added. A second apple-flavored drink was made with this solution, which contained 0.3 g of the solution contained per 1 finished drink.

In a comparison of the two drinks by a group of experienced taste experts, the drink with the addition Unanimously preferred by ethyl saffron.

Example 7

Preparation of a raspberry flavored composition.

A raspberry flavored composition was made by mixing the following ingredients:

Geraniol 20th Vanillin 20th Maltol 20th Phenylethyl alcohol 50 p-hydroxybenzyl acetone 50 c £ -Methyljonon 100 p-ionone 100 Benzyl acetate 100 Isobutyl acetate 100 Ethyl acetate 100 Amyl acetate 100 Ethanol 240

'C Ü y b ά D / ι U / hi ι. * - -

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DIPL.-INQ. DIETER JANDER DR-INQ. MANFRED BONINQ

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A 1 # solution of this mixture in ethanol was used as a flavor used in a raspberry drink. The addition of 100 ppm ethyl saffronate to the ethanol solution resulted in a improved drink with a natural raspberry-like taste and smell.

Example 8

Manufacture of a composition with a mimicked raspberry flavor. A composition with mimicked raspberry flavor was made produced as a modification of the instructions by L. Benezet, La Parfumerie Moderne 43 (1951) No. 22, 61-78:

Acetylmethyl carbinol 3 Diacetyl 2 Ethyl acetate 10 Isobutyl acetate 40 Ethyl hexanoate 10 Isoamyl hexanoate 10 Hexyl acetate 10 Hexenyl acetate 10 Benzyl acetate 50 Isoamyl alcohol 10 Hexanol 5 Hexenol 5 ß-Jonon 25th a, -Methyl ^ onone 25th Iris oil (heavy) 15th Anisaldehyde 5 Benzaldehyde 5 Phenylethyl alcohol 50 Methyl salicylate 10 Bornyl alicylate 10 Clove germ oil 10 Orange oil, sweet 50 Geranium oil 10 Coumarin 20th Vanillin 30th 509336 / 102S

DIPL-INq. DIETER JANDER DR.-INQ. MANFRED BONINC

PATENT LAWYERS 2508Ü59

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so called "Aldehyde C-16" 400 Benzylidene mesity oxide 100

Ethyl benzoate 10

940

0.3 g of a 1 # solution in ethanol were used per 1 finished drink used.

The addition of 100 ppm ethyl saffronate to the ethanol solution of the flavor composition resulted in a beverage with a better raspberry flavor.

Example 9

Rose-type perfume composition

Three rose-type compositions became the following by mixing Components manufactured:

Composition Compound A BC

Cinnamon alcohol trichloromethylphenylcarftinylacetate phenylethyl alcohol Rhodinol Citronellol Nerol

Phenylacetaldehyde dimethylacetal cL- methyl ionone guaiyl acetate hydroxycitronellal

Gyrane (N), fragrance available from Naarden International N.V.

Phenylethyl propionate Geranyl Acetate Citronelly Ethyl Oxalate Geranium Oil Bourbon

Rose oxide, 10 # solution in diallyl phthalate 15

Roeana NB 131, Roeenbaee available from Naarden International N.V.

Rose absolute 5 5

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15th 10 20th 5 5 - 355 370 365 180 160 170 170 140 120 20th 40 70 30th 40 30th 10 10 10 10 5 10 10 15th 17th 30th 25th 20th 20th 25th 15th 10 10 5 20th 25th 35 20th 20th 15th 15th 10 5 60 70 80

DIPL-INQ. DIETER JANDER DR-INQ. MANFRED BONINQ

PATENT Attorneys ^ 5 0 8 0 5 S

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Three modifications "were prepared from composition A:

a) Addition of 1g of a 10 # solution of our in Example 8 British Patent Application No. 08165/74 described Damascone homologues in diethyl phthalate to 98.5 g of the masterbatch A. ■

b) Addition of 0.5g of a 1% solution of ethyl saffron in Diethyl phthalate to 98.5 g of the basic mixture A.

c) Addition of both 1g of the solution according to a) and 0.5g of the Solution according to b) to 98.5 g of the basic mixture A.

Three modifications were made of composition B:

a) Addition of 1 g of a 1096 solution of our in Example 9 British patent application No. 08165/74 specified Damascenone homologues in diethyl phthalate to 98.5 g of the basic mixture B.

b) Addition of 0.5g of a 1 # solution of ethyl saffron in Diethyl phthalate to 98.5 g of the basic mixture B.

c) Addition of both 1g of the solution according to a) and 0.5g of the solution according to b) to 98.5g of the basic mixture B.

Finally, there were three modifications of Composition C manufactured:

a) Addition of 0.5g of a 10bigen solution of / 3-Damascenon in Diethyl phthalate to 99.2 g of the basic mixture C.

b) addition of 0.3 g of a 1 # solution of ethyl saffron in Diethyl saffronate to 99.2 g of the basic mixture C.

c) addition of both 0.5 g of the β-damascenone solution as well 0.3g of the ethyl saffronate solution to 99.2g of the basic mixture C.

A group of 10 trained fragrance experts were asked to compare the modifications with the starting mixtures. In each case it was found that the basic mixture was improved by adding the cycloaliphatic ketones (additives a) or by adding ethyl saffronate (additives b). In

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DIPL-INC /. DIETER JANDER DR.-INO- MANFRED BONINC

PATENT LAWYERS 2 5 O 8 O 5 9

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In all three cases, however, the conclusion was reached that the addition of both additives (a + b) made the effects superadditive were and compositions with a very natural rose character which had a radiant warmth and a well-balanced top note.

Example 10

Apple flavor imitation.

Three modifications of the basic composition of Example 5 were made:

A. To 100 g of the basic mixture was added 2.5 g of a 1 # solution of / 3-damascenone given in ethanol.

B. 5 g of a 1% solution were added to 100 g of the starting mixture given by ethyl saffron in ethanol.

C. 2.5 g of a 1 # solution were added to 100 g of the basic mixture of β-damascenone in ethanol and 5g of a 1% solution of Put ethyl saffronate in ethanol.

These three modifications of the base mix were used in finished apple beverages by a group of seasoned flavor experts judged. According to the statements of this group, the modifications A and B already showed an improvement in the basic composition; the beverage containing modification C became but far preferred. This modification gave the drink an even more natural taste and fragrance than A and B.

The apple flavor imitations of Example containing 5 »the 25 or 50 ppm Äthylsafranat, and the modification C of this example can be used to impart tobacco products taste as in ⁿ Merory, Food Flavorings, Composition, Manufacture and Use, Westport 1968 "is described.

Example 11

Raspberry flavor imitation.

Three modifications of the basic composition of Example 8 were made:

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DIPL-INQ. DIETER JANDER DR-INQ. MANFRED BONINNC

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A. 10g of the basic mixture was dissolved in 1000g of ethanol x 0.2g Ethyl saffronate was added.

B. 10g of the basic mixture were dissolved in 1000g of ethanol and 0.1g of a 1oil solution of the Damascenon homologue of the Example 9 of British patent application 08165/74 added in ethanol.

C. 10g of the basic composition was dissolved in 1000g of ethanol and 0.2g ethyl saffronate and 0.1g of a 1Obigen solution of the Damascenone homologues of example 9 of British patent application 08165/74 in ethanol were added.

From these three modifications and from the basic composition, beverages with a raspberry flavor were made by each 0.3g of the alcoholic solutions were used per 1 finished drink. The beverages were prepared by a group of skilled flavor experts compared to each other. Although the drinks made with the help of modifications A and B. were considered to be improvements over the beverage made from the base composition there was a unanimous preference for the drink made from mixture C. In the drinks that made the basic mixture or the modifications A or B are made, the smell and taste of ^ -Jonon can be clearly determined. The drink, which is made from modification C, is much more rounded in taste and smell and has a strong raspberry character.

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509836/1026

Claims (8)

Patent sayings /1.)3af ransäureester of the general formula IV COOR, ^IT 5 "1 wherein the dashed lines two conjugated double bonds in the positions 2-endocyclic and 4- ( ⁰ C-isomer), 1 and 3
(& -isomer) or 2-exocyclic and 3 ('/' - isomer) and Ry, an alkyl group or in the ^ -isomer an alkylidene group each with 1-3 carbon atoms and R ₂ denotes an alkyl or alkenyl group with 1-4 carbon atoms, with the exception of the compounds in which RyJ = CH, or OHp and Rp = GH, or CpH, -. 2. A process for the preparation of fragrance or flavor compositions, characterized in that one or more lister of the general formula _{χ ay} IV wherein the dashed lines two conjugated double bonds in the positions 2-endocyclic and U- (pC -isomer), 1 and 3
(^ -isomer) or 2-exocyclic and 3 (^ -isomer) represent and Ry, an alkyl group or in the ^ -isomers an alkylidene group each having 1-3 carbon atoms and R ₂ denotes an alkyl or alkenyl group with 1-4 carbon atoms, as a fragrance or flavoring substance together with other ingredients that are added to such compositions - / ground,
uses v / earth. 3. The method according to claim 2, wherein together with the (the) 509836/1026 DIPU-INQ. DIETER JANDER DR.-INQ. MANFRED BONINQ PATENTANWÄLTE 2 5 0 8 U D v3 - 27-. ^ ster (s) according to the formula IV an effective! close of Danascon (s) and / or Damascenon (s) and / or analogues according to British Patent 1,240? O9 and the Netherlands Patent application 72'.Tl248 and / or by homologues and / or Analogously according to British patent application 8165 / 74- is added. 4. The method according to claim 3, characterized in that that the quantities of the third (s) and the quantities of the other substances are in a ratio of about 1: £ o to about Ao: 1. 5. A process for the preparation of / erbindungen of the formula IV, mainly from ethyl-öjö-dimethyl ^ -alkylidene ^ -cyclohexencarboxylate exist, characterized in that Ii.thyl-6,6-dimethyl ^ -äthyl - ^ - oxo-S-cyclohexenecarboxylate with p-Toluenesulfonic acid is refluxed for 2 to 7 hours. 6. Fragrance or flavor composition containing one or more esters of the formula IV, in which the dashed lines have two conjugated double bonds in the positions 2-endocyclic and 4 (σί-isomer), 1 and 3 - isomer) or 2-exocyclic and 3 ("/" -isomer) represent and Ry, an alkyl group or in the ^ - -isomers an alkylidene group each having 1-3 carbon atoms and R _{2 represents} an alkyl or alkenyl group with 1-4 carbon atoms, if desired in combination with an effective range of damascone (s) and / or damascenone (s) according to British patent 1 24o 3o9 and Dutch patent application 72.11248 and / or the homologues and / or analogs according to British patent application 8165/74. 7. Fragrance or flavor composition as in US Pat Examples 2-11 described. - 28 - 509836/1026 DIPL-INO. DIETER JANDER DR.-INQ. MANFRED BONING O r00 0 CQ PATENT LAWYERS tJUOU J J 8. Process for the manufacture of perfumed articles, characterized in that one or more ■ second of the formula IV are used. 9 · Perfumed article presented by a process according to claim 6. 509836/1026